DE10029462A1 - New water soluble polymers based on macromonomer with polyalkylene oxide units, useful as adjuvants in cosmetic, pharmaceutical and agrochemical compositions - Google Patents

Abstract

Water soluble polymers produced by copolymerization of macromonomers based on polyalkylene oxides are new. Water soluble polymers produced by copolymerization of macromonomers based on polyalkylene oxides are new. The polymers are produced by the radical copolymerization of: (A) macromonomer(s) containing a terminal group capable of polymerisation, a hydrophilic part based on polyalkylene oxides and a hydrophobic part comprising H or upto 30C hydrocarbon group and (B) olefinically unsaturated comonomer(s) containing O, N, S P Cl and/or F. An Independent claim is also included for aqueous, aqueous-alcoholic and aqueous-tensidic preparations, emulsions and suspensions containing the polymers.

Description

The present invention relates to water soluble polymers made by Copolymerization of macromonomers, and their use in cosmetic and pharmaceutical agents.

In recent years, water-soluble polymers have become increasingly larger growing importance in industry and science. Polyelectrolytes take it in terms of quantity a very large part of the total annual production water-soluble polymers. They are used as flocculants in the Paper processing, the detergent industry, textile processing, as Protective colloids or in their networked variants as thickeners, to name just a few To name areas of application.

Thickeners, especially those based on polyacrylic acid "Superabsorbers" have been made in Germany since their development in the 1970s Hygiene area is indispensable. Newer thickeners, such as the cross-linked one Polyacrylamidopropylene methyl sulfonic acid (or its salts) are characterized by their significantly improved pH stability and better processability.

For the purpose of simplifying cosmetic preparations, the last Years increasingly looked for raw materials that have multiple properties in one Combine formulation ingredient. Pure "thickeners" are replaced by new ones Substances detached, for example, in their property profile Have emulsifier properties and thus an addition of separate Make emulsifiers unnecessary in formulations. The synthesis of the following The polymers described offer the ideal instrument for this. The interesting one Combination of a polyelectrolyte (e.g. poly-AMPS) with non-polar parts of the molecule offers the possibility of varying the hydrophilic-hydrophobic balance of a  Polymers like those used in synthetic polymer chemistry only in a few cases is observed.

The temperature behavior of the polymers is an important property. in the in general, polymers show high viscosity at low temperatures, and low viscosity at high temperatures. Often, however, are desired such polymers that have a thickening effect above certain temperatures, but at remain pumpable and processable at low temperatures in solution.

EP-A-0 583 814 and EP-A-0 629 649 disclose polymers based on acrylic acid as main chain and polyethylene and / or polypropylene glycols as side chains. These polymers show a thickening with increasing temperatures.

All attempts to produce such polymers on an industrial scale were successful so far unsuccessful. In addition, the use of acrylic acid was Main chain polymers necessary for the realization of the concept of thermo-thickening polymer solutions in water. One of the most serious Problems with this class of polymer are precipitation phenomena due to Instabilities towards divalent ions.

In the present invention there is now a new class of polymers and a process described for their manufacture. It can be done with little preparation work this process based on a radical copolymerization, in particular the Precipitation polymerization, possible to use a variety of new polymers different thermal solution behavior on an industrial scale to manufacture.

Surprisingly, it was found that polymers that mentioned Requirements are sufficient, can also be represented by means of a macromonomer synthesis are. This has the consequence that the required according to the prior art Definition of acrylic acid as one of the main chain monomers is dropped.  

The invention relates to water-soluble polymers which can be prepared by radical copolymerization of

• A) one or more macromonomers containing an end group capable of polymerization, a hydrophilic part which is based on polyalkylene oxides, and a hydrophobic part which is hydrogen or a saturated or unsaturated, linear or branched, aliphatic, cycloaliphatic or aromatic (C ₁ -C ₃₀ ) -hydrocarbon residue includes, and
• B) one or more olefinically unsaturated comonomers which contain oxygen, Contain nitrogen, sulfur, phosphorus, chlorine and / or fluorine.

The macromonomers A) are preferably those of the formula (1)

R ¹ -Y- (R ² -O) _x -R ³ (I)

wherein R ^{1 is} a vinyl, allyl, acrylic or methacrylic radical; R ² (C ₂ -C ₄ ) alkylene; x is an integer between 1 and 500; Y = O, S, PH or NH; and R ^{3 is} hydrogen or a saturated or unsaturated linear or branched aliphatic, cycloaliphatic or aromatic (C ₁ -C ₃₀ ) hydrocarbon radical.

R ¹ particularly preferably represents an acrylic or methacrylic radical. R ² particularly preferably represents an ethylene or propylene radical. x particularly preferably stands for a number between 3 and 50, particularly preferably for a number between 7 and 30. R ³ is preferably aliphatic or cycloaliphatic hydrocarbons, which can be saturated or unsaturated. R ³ particularly preferably represents a (C ₆ -C ₂₂ ) hydrocarbon radical, particularly preferably a (C ₁₂ -C ₁₈ ) hydrocarbon radical.

The macromonomers are generally prepared by the reaction reactive derivatives of (meth) acrylic acid containing hydroxyl groups Compounds, especially alkoxylated alkyl radicals. Even the ring opening Addition to (meth) acrylic acid glycidyl ester is possible.  

Suitable olefinically unsaturated comonomers B) are preferably olefinically unsaturated acids and their salts with mono- and divalent counterions, particularly preferably styrene sulfonic acid, acrylamidopropyl methylene sulfonic acid (AMPS), vinyl sulfonic acid, vinyl phosphonic acid, allylsulfonic acid, Methallylsulfonic acid, acrylic acid, (meth) acrylic acid, maleic acid or Maleic anhydride and its salts; Esters of acrylic and (meth) acrylic acid with aliphatic, aromatic or cycloaliphatic alcohols with a Carbon number from 1 to 22; Esters of acrylic and (meth) acrylic acid with Alkyl ethoxylates, open-chain and cyclic N-vinyl amides (N-vinyl lactams) with one Ring size of 4 to 9 atoms, particularly preferably N-vinylformamide (NVF), N-vinylmethylformamide, N-vinyl-methylacetamide (VIMA), N-vinylacetamide, N-vinyl pyrrolidone (NVP) and N-vinyl caprolactam; Amides the acrylic and the Methacrylic acid, particularly preferably acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, alkoxylated acrylic and methacrylamides, such as. B. MAPTAC and APTAC; 2-vinyl pyridine; 4-vinyl pyridine; Vinyl acetate; Methacrylic acid glycidyl ester; Acrylonitrile; Vinyl chloride; Vinylidene chloride; Tetrafluoroethylene and / or DADMAC.

Suitable counterions for the salts of the olefinically unsaturated acids are preferably lithium, sodium, potassium, magnesium, calcium, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium, the alkyl substituents of the ammonium ions being independently (C ₁ -C ₂₂ ) -alkyl radicals which can be occupied by 0 to 3 hydroxyalkyl groups, the alkyl chain length of which can vary in a range from C ₂ to C ₁₀ . One to three times ethoxylated ammonium compounds with different degrees of ethoxylation are also suitable. Sodium and ammonium are particularly preferred as counterions. The degree of neutralization of the olefinically unsaturated acids is preferably 70 and 100 mol%.

Water-soluble polymers which can be prepared by free-radical copolymerization of are particularly preferred

• A) one or more macromonomers selected from the group of the esters of (meth) acrylic acid with alkyl ethoxylates, which comprise 5 to 80 EO units and (C ₁₀ -C ₂₂ ) alkyl radicals, and
• B) one or more olefinically unsaturated comonomers selected from the group of acrylamidopropylmethylene sulfonic acid (AMPS), sodium and Ammonium salts of acrylamidopropylmethylene sulfonic acid (AMPS), acrylamide, N-vinyl formamide, N-vinyl methylacetamide and / or sodium methallyl sulfonate.

Particularly suitable macromonomers A) are esters of (meth) acrylic acid
(C ₁₀ -C ₁₈ ) fatty alcohol polyglycol ether with 8 EO units (Genapol® C-080)
C ₁₁ oxo alcohol polyglycol ether with 8 EO units (Genapol® UD-080)
(C ₁₂ -C ₁₄ ) fatty alcohol polyglycol ether with 7 EO units (Genapol® LA-070)
(C ₁₂ -C ₁₄ fatty alcohol polyglycol ether with 11 EO units (Genapol® LA-110)
(C ₁₆ -C ₁₈ ) fatty alcohol polyglycol ether with 8 EO units (Genapol® T-080)
(C ₁₆ -C ₁₈ ) fatty alcohol polyglycol ether with 15 EO units (Genapol® T-150)
(C ₁₆ -C ₁₈ ) fatty alcohol polyglycol ether with 11 EO units (Genapol® T-110)
(C ₁₆ -C ₁₈ ) fatty alcohol polyglycol ether with 20 EO units (Genapol® T-200)
(C ₁₆ -C ₁₈ ) fatty alcohol polyglycol ether with 25 EO units (Genapol® T-250)
(C ₁₈ -C ₂₂ ) fatty alcohol polyglycol ether with 25 EO units
and / or iso (C ₁₆ -C ₁₈ ) fatty alcohol polyglycol ether with 25 EO units
and the olefinically unsaturated comonomers B) are in particular the sodium and ammonium salts of acrylamidopropylmethylene sulfonic acid (AMPS). The Genapol® types are products from Clariant.

The molar proportions of the macromonomers A) and the comonomers B) in the polymer can vary between 0.1 and 99.9 mol%.

In a preferred embodiment (highly hydrophobically modified polymers) The proportion of macromonomers A) is 50.1 to 99.9 mol%, preferably 70 to 95 mol%, particularly preferably 80 to 90 mol%.

In a further preferred embodiment (low hydrophobically modified Polymers), the proportion of macromonomers A) is 0.1 to 50 mol%, preferably 5 to 25 mol%, particularly preferably 10 to 20 mol%.  

The monomer distribution of the macromonomers A) and comonomers B) in the Polymers can, for example, alternate, block-like (also multiblock) or be statistical (also gradient).

The polymers generally have a number average molecular weight of 1000 up to 20,000,000 g / mol, preferably 20,000 to 5,000,000, particularly preferably 100,000 to 1,500,000 g / mol.

In a preferred embodiment, the polymers according to the invention networked, d. H. they contain at least one crosslinker with at least two Double bonds that are polymerized into the polymer. Suitable crosslinkers are in particular methylene bisacrylic and methacrylamide, esters of unsaturated mono- or Polycarboxylic acids with polyols, e.g. B. diacrylates or triacrylates, such as. B. butanediol and ethylene glycol diacrylate or methacrylate and trimethylolpropane triacrylate, Allyl compounds such as e.g. B. allyl (meth) acrylate, triallyl cyanurate, Maleic acid diallyl ester, polyallyl ester, tetraallyloxyethane, triallylamine, Tetraallylethylenediamine, allyl esters of phosphoric acid and / or Vinylphosphonic acid derivatives.

A preferred embodiment of the invention are those polymers which from a water-soluble polymer skeleton and macromonomers A) heat-sensitive side chains that have an LCST behavior in water, exist, and the aqueous solution has a viscosity that above a certain threshold temperature increases with increasing temperature or approximately remains constant.

Such polymers represent a further preferred embodiment of the invention represents, whose aqueous solution has a viscosity below a first Threshold temperature is low, above this first threshold temperature with increasing temperature increases to a maximum and above a second Threshold temperature drops again with increasing temperature. It is preferred that the viscosity of the polymer solutions below the first threshold temperature at 5 to 50%, in particular 10 to 30%, of the maximum viscosity in the second Threshold temperature.  

Such polymers are also a preferred embodiment of the invention represents, whose aqueous solutions have a high viscosity and at room temperature have no thermo-associative behavior.

The viscosities of the 1% strength aqueous solutions are preferably 20,000 mPas up to 100,000 mPas, in particular 60,000 mPas to 70,000 mPas.

Such polymers show a high thickening performance even at room temperature, good emulsifying properties and good dispersion properties in aqueous, aqueous-alcoholic and aqueous-surfactant solution or in emulsions. Preparations containing such polymers also show good results Transparency and high electrolyte stability.

The polymers according to the invention are obtained by radical copolymerization, such as e.g. B. precipitation polymerization, emulsion polymerization, solution polymerization or Suspension polymerization produced. Precipitation is preferred polymerization, particularly preferably the precipitation polymerization in tert-butanol.

With the help of precipitation polymerization in tert-butanol, one for the Use of the polymers particularly favorable particle size distribution Achieve polymers. The size distribution of the polymer particles can e.g. B. by Laser diffraction or sieve analysis can be determined. Representative of a cheap Size distribution is the following grain size distribution as seen through sieve analysis for an AMPS copolymer was determined: 60.2% smaller than 423 micrometers, 52.0% less than 212 microns, 26.6% less than 106 microns, 2.6% less than 45 microns and 26.6% larger than 850 microns.

The polymerization reaction can take place in the temperature range between 0 and 150 ° C, preferably between 10 and 100 ° C, both at normal pressure and below increased or reduced pressure can be carried out. As usual, the Polymerization also in a protective gas atmosphere, preferably under nitrogen, be carried out.

To initiate the polymerization, high-energy electromagnetic radiation or the usual chemical polymerization initiators can be used, e.g. B. organic peroxides, such as benzoyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, cumene hydroperoxide, azo compounds, such as. B. azobisisobutyronitrile, azobisdimethylvalerionitrile, and inorganic peroxy compounds, such as. B. (NH ₄ ) ₂ S ₂ O ₈ , K ₂ S ₂ O ₈ or H ₂ O ₂ , optionally in combination with reducing agents, such as. B. sodium bisulfite and iron (II) sulfate, or redox systems, which as a reducing component an aliphatic or aromatic sulfonic acid, such as. B. benzenesulfonic acid, toluenesulfonic acid or derivatives of these acids, such as. B. Mannich adducts of sulfinic acid, aldehydes and amino compounds.

The polymers according to the invention are suitable as thickeners and dispersants for aqueous preparations, aqueous-alcoholic and aqueous-surfactant Preparations and as emulsifiers, suspending agents with thickening action and Consistency generator for emulsions and suspensions. You can do that too Mixtures of the polymers are used. The are particularly suitable Polymers for use in cosmetic and pharmaceutical compositions. It is important that the polymers are used without the use of an additional co- Emulsifier and / or without the use of an additional consistency agent can be used. The use of co-emulsifiers and Consistency generators are therefore not mandatory, but possible.

The invention thus also relates to aqueous preparations, aqueous alcoholic preparations, aqueous surfactant preparations, emulsions and Suspensions containing the polymers according to the invention.

The preparations, emulsions and suspensions are preferred to cosmetic and pharmaceutical agents, such as. B. shampoos, shower baths, Shower gels, foam baths, gels, lotions, creams and ointments.

The preparations, emulsions and suspensions according to the invention contain based on the finished formulation, preferably 0.05 to 10 wt .-%, particularly preferably 0.1 to 5% by weight, particularly preferably 0.5 to 3% by weight polymers according to the invention.

The polymers according to the invention can be used as thickeners for agents on aqueous or aqueous-alcoholic basis, for example hair gels, are used. Of  the polymers according to the invention are also suitable as thickeners, Dispersant and consistency agent for aqueous surfactant preparations, for example shampoos, shower baths, shower gels, foam baths and the like. The thickening effect of the polymers according to the invention in aqueous surfactants It is averaged through an association of the polymer side chains and the surfactants reinforced and can by the choice of the side chains of the polymers and by the Choice of surfactants can be controlled. The suspending or dispersing and Stabilizing effect of the polymers according to the invention in aqueous surfactants Is averaged through the association of the polymer side chains and the insoluble liquid components, for example silicone oils, or the insoluble components, for example zinc pyrethione.

The agents according to the invention can all be used as further auxiliaries and additives usual anionic, cationic, zwitterionic, nonionic and amphoteric surfactants, as well as other additives commonly used in cosmetics, such as. B. Superfatting agents, stabilizers, biogenic agents, glycerin, Preservatives, pearlescent agents, colors and fragrances, solvents, Opacifiers, other thickeners and dispersants, further Protein derivatives such as gelatin, collagen hydrolyzates, polypeptides on natural and synthetic base, egg yolk, lecithin, lanolin and lanolin derivatives, fatty alcohols, Silicones, deodorants, fabrics with keratolytic and keratoplastic Effect, contain enzymes and carriers. Furthermore, the agents according to the invention antimicrobial agents are added.

The total amount of the surfactants used in the compositions according to the invention, based on the finished composition, can be between 5 and 70% by weight, preferably between 10 and 40% by weight, particularly preferably between 12 and 35% by weight. The following may be mentioned as anionic detergent substances: (C ₁₀ -C ₂₀ ) -alkyl and alkylene carboxylates, alkyl ether carboxylates, fatty alcohol sulfates, fatty alcohol ether sulfates, alkyl amide sulfates and sulfonates, fatty acid alkyl amide polyglycol ether sulfates, alkane sulfonates and hydroxyalkanesulfonates, olefinsulfonate, isolefinsulfonates, isocyanate sulfonates, isocyanate sulfonates, isocyanate sulfonates, olefinsulfonates, isolefinsulfonates, isocyanate sulfonates, isocyanate sulfonates, isocyanate sulfonates, isolefinsulfonates, isocyanate sulfonates, isolefinsulfonates, isolefinsulfonates, isolefinsulfonates, isolefinsulfonates, isolefinsulfonates, isolefinsulfonates, and isocyanate sulfonates, Alkylphenol glycol ether sulfonates, sulfosuccinates, sulfosuccinic acid semiesters and diesters, fatty alcohol ether phosphates, protein fatty acid condensation products, alkyl monoglyceride sulfates and sulfonates, alkyl glyceride ether sulfonates, fatty acid methyl taurides, fatty acid sarcosinates, sulforicglutolamates, sulforicglutolamates. These compounds and their mixtures are used in the form of their water-soluble or water-dispersible salts, for example the sodium, potassium, magnesium, ammonium, mono-, di- and triethanolammonium and analogous alkylammonium salts.

The proportion by weight of the anionic surfactants in the agents according to the invention is preferably in the range from 7 to 30% by weight, particularly preferably 10 to 25% by weight, particularly preferably 12 to 22% by weight.

Suitable cationic surfactants are, for example, quaternary ammonium salts such as di (C ₁₀ -C ₂₄ ) alkyl dimethyl ammonium chloride or bromide, preferably di (C ₁₂ -C ₁₈ ) alkyl dimethyl ammonium chloride or bromide; (C ₁₀ -C ₂₄ ) alkyl dimethyl ethyl ammonium chloride or bromide; (C ₁₀ -C ₂₄ ) alkyl trimethyl ammonium chloride or bromide, preferably cetyl trimethyl ammonium chloride or bromide and (C ₂₀ -C ₂₂ ) alkyl trimethyl ammonium chloride or bromide; (C ₁₀ -C ₂₄ ) alkyl dimethylbenzyl ammonium chloride or bromide, preferably (C ₁₂ -C ₁₈ ) alkyl dimethylbenzyl ammonium chloride; N- (C ₁₀ -C ₁₆ ) alkyl pyridinium chloride or bromide, preferably N- (C ₁₂ -C ₁₆ ) alkyl pyridinium chloride or bromide; N- (C ₁₀ -C ₁₈ ) alkyl isoquinolinium chloride, bromide or monoalkyl sulfate; N- (C ₁₂ -C ₁₈ ) alkyl polyoylaminoformylmethyl pyridinium chloride; N- (C ₁₂ -C ₁₈ ) alkyl-N-methylmorpholinium chloride, bromide or monoalkyl sulfate; N- (C ₁₂ -C ₁₈ ) alkyl-N-ethyl-morpholinium chloride, bromide or monoalkyl sulfate; (C ₁₆ -C ₁₈ ) alkyl pentaoxethyl ammonium chloride; Diisobutyl phenoxyethoxyethyldimethylbenzylammonium chloride; Salts of N, N-diethylaminoethylstearylamide and oleylamide with hydrochloric acid, acetic acid, lactic acid, citric acid, phosphoric acid; N-acylaminoethyl-N, N-diethyl-N-methyl ammonium chloride, bromide or monoalkyl sulfate and N-acylaminoethyl-N, N-diethyl N-benzylammonium chloride, bromide or monoalkyl sulfate, with acyl preferably represents stearyl or oleyl.

The proportion by weight of the cationic surfactants in the agents according to the invention is preferably in the range from 1 to 10% by weight, particularly preferably 2 to 7% by weight, particularly preferably 3 to 5% by weight.

As non-ionic surfactants used as detergent substances can be considered, for example: fatty alcohol ethoxylates (Alkyl polyethylene glycols); Alkylphenol polyethylene glycols; Alkyl mercaptan polyethylene glycols; Fatty amine ethoxylates (Alkylaminopolyethylene glycols); Fatty acid ethoxylates (acyl polyethylene glycols); Polypropylene glycol ethoxylates (Pluronics®); Fatty acid alkylolamides, (Fatty acid amide polyethylene glycols); N-alkyl-, N-alkoxypolyhydroxy fatty acid amide, Sucrose esters; Sorbitol ester and the polyglycol ether.

The proportion by weight of the nonionic surfactants in the agents according to the invention is preferably in the range from 1 to 20% by weight, particularly preferably 2 to 10%, particularly preferably 3 to 7% by weight.

Preferred amphoteric surfactants are: N- (C ₁₂ -C ₁₈ ) -alkyl-β-aminopropionate and N- (C ₁₂ -C ₁₈ ) -alkyl-β-iminodipropionate as alkali and mono-, di- and trialkylammonium salts; N-acylaminoalkyl-N, N-dimethyl-acetobetaine, preferably N- (C ₈ -C ₁₈ ) -acyl aminopropyl-N, N-dimethylacetobetaine; (C ₁₂ -C ₁₈ ) alkyl dimethyl sulfopropyl betaine; Amphoteric surfactants based on imidazoline (trade name: Miranol®, Steinapon®), preferably the sodium salt of 1- (β-carboxymethyloxyethyl) -1- (carboxymethyl) -2-lauryl-imidazolinium; Amine oxide, e.g. B. (C ₁₂ -C ₁₈ ) alkyl dimethylamine oxide, fatty acid amidoalkyl dimethylamine oxide.

The proportion by weight of the amphoteric surfactants in the agents according to the invention is preferably in the range from 0.5 to 20% by weight, particularly preferably 1 to 10% by weight.

Furthermore, foam-enhancing agents can be used in the agents according to the invention Co-surfactants from the group alkyl betaines, alkyl amido betaines, aminopropionates, Aminoglycinates, imidazolinium betaines and sulfobetaines, amine oxides and Fatty acid alkanolamides or polyhydroxyamides are used.  

Preferred surfactants in the agents according to the invention are lauryl sulfate, Laureth sulfate, cocoamidipropyl betaine, sodium cocoyl glutamate, Disodium laureth sulfosuccinate and coconut fatty acid diethanolamide.

The preparations according to the invention can also be used in cosmetics common additives such as superfatting agents, stabilizers, biogenic agents, Glycerin, preservatives, pearlescent agents, colors and fragrances, solvents, Opacifiers, thickeners and dispersants also protein derivatives such as Gelatin, collagen hydrolyzates, polypeptides on a natural and synthetic basis, Egg yolk, lecithin, lanolin and lanolin derivatives, fatty alcohols, silicones, deodorants Agents, substances with keratolytic and keratoplastic effects, enzymes and Carrier substances included. Furthermore, the agents according to the invention antimicrobial agents are added.

Substances such as polyethoxylated can be used as superfatting agents Lanolin derivatives, lecithin derivatives, polyol fatty acid esters, monoglycerides and Fatty acid alkanolamides are used, the latter being used simultaneously as Foam stabilizers are used. Typical examples of fats are glycerides, as Waxes come u. a. Beeswax, paraffin wax or micro waxes, optionally in combination with hydrophilic waxes, e.g. B. Cetylstearyl alcohol in Question.

Metal salts of fatty acids, such as. B. magnesium, Aluminum and / or zinc stearate can be used.

Plant extracts and Understand vitamin complexes.

Suitable preservatives are, for example, phenoxyethanol, Formaldehyde solution, parabens, pentanediol or sorbic acid.

Examples of pearlescent agents are glycol distearic acid esters, such as Ethylene glycol distearate, but also fatty acid monoglycol esters into consideration.

Suitable dyes are those which are suitable and approved for cosmetic purposes Substances are used.

Other suitable thickeners are sodium, potassium, ammonium chloride, sodium sulfate, fatty acid alkylolamides, cellulose derivatives, for example hydroxyethyl cellulose, guar gum, polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropyl guar gum, starch and starch derivatives and natural gums, carboxyvinyl polymers, for example Carbopol - 934, -940 941, -956, -980, -981, -1342, -1382, ethylene glycol esters of fatty acids with 14 to 22, particularly preferably 16 to 22, carbon atoms, in particular mono- and di-ethylene glycol stearate. Also preferred are stearin monoethanolamide, stearin diethanolamide, stearin isopropanolamide, stearin monoethanol amide stearate, stearyl stearate, cetyl palmitate, glyceryl stearate, stearamide diethanolamide distearate, stearamide monoethanol amide stearate, N, N-dihydrocarbyl) and especially ( _16- benzocarbyl) (C ₁₆ -solobenzoyl), ( ₁₂ ) -solobenzoyl ( ₁₈ ) -sulfonyl (C) -12-hydrocarbyl), and in particular ( _16- C- _22- hydrocarbyl), (C) , N-di (C ₁₆ -C ₁₈ ) amido benzoic acid and its derivatives.

The dispersants are, based on the finished agent, in concentrations of preferably 0.5 to 10% by weight, particularly preferably 0.5 to 5% by weight, particularly preferably from 1 to 4% by weight.

The desired viscosity of the agent can be added by adding water and / or organic solvents or by adding a combination of organic Solvents and thickeners can be adjusted.

In principle, all mono- or polyvalent come as organic solvents Alcohols into consideration. Alcohols with 1 to 4 carbon atoms such as Ethanol, propanol, isopropanol, n-butanol, i-butanol, t-butanol, glycerin and Mixtures of the alcohols mentioned. Other preferred alcohols are polyethylene glycols with a molecular weight below 2000. In particular is a use of polyethylene glycol with a molecular weight between 200 and 600 and in amounts up to 45% by weight and of polyethylene glycol with a relative molecular mass between 400 and 600 in amounts of 5 to 25% by weight prefers. Other suitable solvents are, for example, triacetin (Glycerol triacetate) and 1-methoxy-2-propanol.

Vegetable oils, natural and hardened, come into consideration as carrier materials Oils, waxes, fats, water, alcohols, polyols, glycerol, glycerides, liquid Paraffins, liquid fatty alcohols, sterol, polyethylene glycols, cellulose and cellulose Derivatives.

Ketoconazole, oxiconazole, terbinafine, bifonazole, Butoconazole, cloconazole, clotrimazole, econazole, enilconazole, fenticonazole,  Isoconazole, miconazole, sulconazole, tioconazole fluconazole, itraconazole, Terconazole, Naftifine and Terbinafine can be used.

Silicones, polyalkylsiloxanes, polyalkylarylsiloxanes, polyethersiloxane copolymers, such as in US 5,104,645 and the publications cited therein, still improve the nourishing effect of the agents according to the invention. The agents according to the invention can with conventional ceramides, pseudoceramides, fatty acid-N- alkylpolyhydroxyalkylamides cholesterol, cholesterol fatty acid esters, fatty acids, Triglycerides, cerebrosides, phospholipids and similar substances, mixed will.

The polymers according to the invention can be used as emulsifiers, stabilizers and / or Consistency agents can be used in emulsions. In particular are for it cross-linked polymers suitable. The emulsions can be both water act in-oil emulsions as well as oil-in-water emulsions.

The emulsifying, stabilizing and / or consistency effect of the Polymers according to the invention in emulsions is by an association of Polymer side chains with each other, as well as through an interaction of the Polymer side chains with the hydrophobic oil components caused or reinforced.

The non-aqueous part of the emulsions, which largely comes from the emulsifier, the thickener and the oil body is usually 5 to 95%, preferably 15 to 75% by weight. It follows that the emulsions 5 to 95 wt .-% and preferably 25 to 85 wt .-% water, depending whether using lotions with a comparatively low or creams and ointments high viscosity to be produced.

The emulsions can be used as skin care products, such as day creams, Night creams, skin care creams, nutritional creams, body lotions, ointments and the like be used and as further auxiliaries and additives, oil bodies, co- Emulsifiers, superfatting agents, fats, waxes, stabilizers, biogenic agents, Contain glycerin, preservatives, colors and fragrances.  

Guerbet alcohols based on fatty alcohols with 6 to 18, preferably 8 to 10 carbon atoms, esters of linear (C ₆ -C ₁₃ ) fatty acids with linear (C ₆ -C ₂₀ ) fatty alcohols, esters of branched (C ₆ - C ₁₃ ) - carboxylic acids with linear (C ₆ -C ₂ o) fatty alcohols, esters of linear (C ₆ -C ₁₈ ) - fatty acids with branched alcohols, especially 2-ethylhexanol, esters of linear and / or branched fatty acids with polyhydric alcohols (such as dimer diol or trimer diol) and / or Guerbet alcohols, triglycerides based on (C ₆ -C ₁₀ ) fatty acids, vegetable oils, branched primary alcohols, substituted cyclohexanes, Guerbet carbonates, dialkyl ethers and / or aliphatic or aromatic hydrocarbons in Consider. The proportion of oil bodies in the non-aqueous proportion of the emulsions can make up 5 to 95 and preferably 15 to 75% by weight.

Suitable nonionic co-emulsifiers are, inter alia, addition products of 0 to 30 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms, with alkylphenols with 8 to 15 carbon atoms in the alkyl group and on sorbitan or sorbitol esters; (C ₁₂ -C ₁₈ ) fatty acid monoesters and diesters of adducts of 0 to 30 moles of ethylene oxide with glycerol; Glycerol monoesters and diesters and sorbitan monoesters and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and, if appropriate, their ethylene oxide addition products; Addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil; Polyol and especially polyglycerol esters, such as. B. Polyglycerol polyricinoleate and polyglycerol poly-12-hydroxystearate. Mixtures of compounds from several of these classes of substances are also suitable.

Suitable ionogenic co-emulsifiers are, for. B. anionic emulsifiers, such as mono-, di- or tri-phosphoric acid esters, but also cationic emulsifiers such as mono-, di- and tri-alkyl quats and their polymeric derivatives.

To the rheological properties of aqueous or solvent-based Adjusting emulsions or suspensions becomes one in the specialist literature Variety of different systems specified. For example, are known Cellulose ethers and other cellulose derivatives (e.g. carboxymethyl cellulose, Hydroxyethyl cellulose), gelatin, starch and starch derivatives, sodium alginates,  Fatty acid polyethylene glycol ester, agar-agar, tragacanth or dextrins. As synthetic polymers different materials are used, such as B. Polyvinyl alcohols, polyacrylamides, polyvinylamides, polysulfonic acids, Polyacrylic acid, polyacrylic acid ester, polyvinyl pyrrolidone, polyvinyl methyl ether, Polyethylene oxides, copolymers of maleic anhydride and vinyl methyl ether, and various mixtures and copolymers from the above Connections, including of their various salts and esters. These polymers can optionally be crosslinked or be non-networked.

The preparation of the emulsions can be carried out in a known manner, i. H. for example by Hot, hot / cold or PIT emulsification take place.

The polymers according to the invention can also be used for the formulation of Plant protection products are used. In this area of application it came in in recent years to rethink the development of new ones Drug formulations. The research for new active ingredients was not in the Foreground, but the search for auxiliary reagents to enhance the effectiveness of known active ingredients on the plant surface. The addition of these so-called Adjuvants enable the amount of active substance used to be reduced Maintaining the effectiveness of the overall formulation compared to adjuvants free wording. Non-polar modified water-soluble polyelectrolytes enable on the one hand an increase in viscosity of the active ingredient solution present - which leads to a slower "beading off" of the leaf surfaces and thus to prolonged exposure to the leaf - and on the other hand, they cause non-polar side residues an increased adsorption on the likewise non-polar Leaf surfaces.

The following examples and applications are intended to explain the invention in more detail, but without restricting it to that.

Examples and applications 1) Representation of the macromonomers a) Variant 1: methacrylic acid glycidyl ester

In a one liter three-necked flask with stirrer, internal thermometer and reflux condenser 600 g of Genapol T-250 are introduced and with 75 g of methacrylic acid glycidyl ester transferred. The reaction mixture is then heated to 100 ° C. for 2 hours and the excess methacrylic acid glycidyl ester was distilled off in vacuo. The The resulting macromonomers can be polymerized without further purification be used.

b) Variant 2: free meth / acrylic acid

In a one liter three-necked flask with stirrer, internal thermometer and reflux condenser 500 g of Genapol UD-070 are presented and with 100 g of meth / acrylic acid and p-Toluenesulfonic acid presented as a catalyst. Then the Reaction mixture boiled under reflux for 2 hours and the excess Acid and the water of reaction formed distilled off in vacuo. The The resulting macromonomers can be polymerized without further purification be used.

c) Variant 3: halogen derivatives of meth / acrylic acid

500 g of Genapol UD-070 with a primary amino end group are placed in a one liter three-necked flask equipped with a stirrer, internal thermometer and reflux condenser and are placed with 110 g of meth / acrylic acid chloride and 50 g of sodium carbonate. The reaction mixture is then boiled under reflux for 2 hours. The cessation of CO ₂ evolution indicates the end of the modification reaction. The excess acid chloride is distilled off in vacuo. The resulting macromonomer with a meth / acrylamide end group can be used in the polymerization without further purification.

d) Variant 4: esters of meth / acrylic acid

In a one liter three-necked flask with stirrer, internal thermometer and reflux condenser 500 g of Genapol LA-090 are introduced and with 100 g of methyl methacrylate and 20 g of titanium tetraisopropylate submitted. Then the reaction mixture Boiled under reflux for 2 hours. After the alcohol is distilled off the remaining ester is distilled off in vacuo. The resulting  Macromonomers with a meth / acrylic acid end group can be used without further purification be used in the polymerization.

2) polymerization General polymerization instructions for the preparation of the invention Side chain polymers after the precipitation process in t-butanol

500 ml of t-butanol are placed in a 2-liter Quickfit flask with reflux condenser, gas inlet, internal thermometer and stirrer and the calculated amount of AMPS is added. The mixture is then neutralized by introducing NH ₃ and the LCST side arms produced as under 1) (several different species also possible) are added to the reaction mixture. If further comonomers are required, these can be added to the reaction mixture after neutralization. After the mixture has been rendered inert with N ₂ or argon, AIBN is added as an initiator at an internal temperature of 60 ° C. and the polymerization reaction is initiated. The finished polymer precipitates after a few minutes. The mixture is heated to reflux for two hours and the polymer is then freed from the solvent on a suction filter and dried in vacuo. This regulation is generally applicable to all polymerization reactions described below.

Side chain polymers with thickening properties

example 1

Reaction according to general polymerization instructions

Example 2

Reaction according to general polymerization instructions

Example 3

Reaction according to general polymerization instructions

Example 4

Reaction according to general polymerization instructions

Example 5

Reaction according to general polymerization instructions

Example 6

Reaction according to general polymerization instructions

Example 7

Reaction according to general polymerization instructions

Example 8

Reaction according to general polymerization instructions

Example 9

Reaction according to general polymerization instructions

Example 10

Polymer blend

Example 11

Reaction according to general polymerisation instructions, however, at 45 ° C start temperature

Example 12

Reaction according to general polymerisation instructions, however, at 45 ° C start temperature

Example 13

Reaction according to general polymerization instructions

Example 14

Reaction according to general polymerization instructions

Example 15

Reaction according to general polymerization instructions

Example 16

Reaction according to general polymerization instructions

Example 17

Reaction according to general polymerization instructions

Comparative Example 1

Comparative Example 1 shows that the temperature at which the viscosification sets in and the strength of the effect can be influenced ( Fig. 1). The polymers used are based on Examples 6, 7 and 8. In addition, a polymer from EP-B-0 583 814 is reproduced. These are pAMPS / 1,2-POE5 from example 1.3. Fig. 1 shows the viscosity of the polymers in aqueous solution. In Fig. 1 it can be seen that the maxima of the viscosification can be found at different temperatures: for example 6 at 120 ° C, for example 7 at 140 ° C and for example 8 at over 200 ° C. pAMPS / 1.2-POE5 has its maximum temperature at 200 ° C. The application concentrations are also significantly lower than with pAMPS / 1.2-POE5 ( Fig. 1).

Fig. 1

Dependence of viscosity on temperature

Furthermore, it can be clearly seen that the polymers according to the invention are based on hydrophobic interaction of the alkyl residues of the side chains Show a basic viscosity at room temperature. pAMPS / 1.2-POE5 forms one Basic viscosity not sufficient. Furthermore, the invention Polymers characterized in that the width of the thermoassociating effect is controllable is.

In the following two examples, the influence of mixtures is different Side arms in a polymer (Example 18) or the influence of mixtures different polymers (Example 19).

Example 18

This example shows the development of the viscosity at different temperatures for the polymers from Example 9. Different side arms are used in one polymer ( Fig. 2).

Fig. 2

Dependence of the viscosity on the temperature for side arm mixtures

Example 19

Fig. 3 shows how the viscosity behavior changes depending on the temperature. Examples 10.1 to 10.3 are different mixing ratios of the polymers from Example 6 and Example 7. The width and strength of the thermoassociating effect can be adjusted via the mixing ratio.

Fig. 3

Viscosity behavior of polymer blends

Examples of oil emulsions

The test emulsions are at 40 ° C, 45 ° C and 50 ° C for a period of Stored for 90 days. 3 different oil mixtures are used each. The Oil mixtures are composed as follows:

Mixture I

Paraffin oil n.a. 50% Isopropyl palmitate 30% Soybean oil 20%

Mixture II

Cetiol V 25% Squalane 25% Myritol 318 25% Isopropyl palmitate 25%

Mixture III

Soybean oil 50% almond oil 20% Avocado oil 20% Jojoba oil 10%

Assessment key

0 = no emulsifier effect
1 = separated in 2 or 3 phases
3 = creaming + oil or water + creaming, homogeneous emulsion in between
4 = water separation, no creaming, no oil separation
5 = oil separation, no creaming, no water separation
6 = creaming
7 = weakly recognizable creaming
8 = practically fine
9 = completely homogeneous emulsion

Emulsifying index

4.1-5.0 = very good
3.1-4.0 = good
2.1-3.0 = medium
1.1-2.0 = bad
0-1.0 = very bad

Test emulsions with crosslinked polymers according to the invention

The stability test shows that the crosslinked polymers according to the invention both as a consistency agent and as an emulsifier with very good Emulsifying properties work. Without additional co-emulsifier and without additional consistency agents will receive stable emulsions.

Formulation examples, all figures in% by weight

Example 41

O / W skin milk

composition

Manufacturing

I: Stir B into A, add C and stir well.
II: Stir D in 1
III: Homogenize the emulsion

Example 42

O / W skin milk

composition

Manufacturing

I: Mix A and B, then add C.
II: Add D to 1
III: Homogenize the emulsion

Example 43

O / W after-sun milk

composition

Manufacturing

I Mix the components of A homogeneously
II Stir CD into I at approx. 35 °.
III Homogenize the emulsion.

Examples of water in oil formulations

Example 44

Reaction according to general polymerization instructions

Example 45

W / O cream

composition

Manufacturing

Melt at 80 ° C
II B heat to 80 ° C.
III Stir II into I.
IV Stir until cool.
V At 35 ° C add C to IV.

Examples of surfactant formulations Example 46

body wash

composition

Manufacturing

Stir IB into A.
II Add components from C successively to I.
III Set pH to 5.5
IV Adjust the viscosity by stirring D into II

Example 47

Baby shampoo

composition

Manufacturing

Solve IB in A.
II adjust pH if necessary

Example 48

Anti-dandruff shampoo, clear

composition

Manufacturing

Mix IA with B.
II Stir C in I until clear solution
III Put components from D one after the other into I.
IV Stir in F while heating and then stir in I.
V Add components from G to I one after the other
VI adjust pH if necessary
VII Adjust the viscosity by stirring H into I.

Example 49

Anti-dandruff shampoo, pearlescent

composition

Manufacturing

I Loosen at 80 ° C in A.
II After cooling to approx. 35 ° C, add components C one after the other

Examples of gels Example 50

Hair gel with conditioning properties

composition

Manufacturing

I Mix components A.
II Mix components B and add to I.
III Give C to D to I.

Example 50

Strong hold hair gel

composition

Manufacturing

I Mix components A.
II Put components B in I.
III Put components C in I.

Claims (16)

1. Water-soluble polymers which can be prepared by radical copolymerization of

• A) one or more macromonomers containing an end group capable of polymerization, a hydrophilic part which is based on polyalkylene oxides, and a hydrophobic part which is hydrogen or a saturated or unsaturated, linear or branched, aliphatic, cycloaliphatic or aromatic (C ₁ -C ₃₀ ) -hydrocarbon residue includes, and
• B) one or more olefinically unsaturated comonomers which contain oxygen, nitrogen, sulfur, phosphorus, chlorine and / or fluorine.

2. Polymers according to claim 1, characterized in that the macromonomers A) are those of the formula (1)
R ¹ -Y- (R ² -O) _x -R ³ (1)
acts, wherein R ^{1 is} a vinyl, allyl, acrylic or methacrylic radical; R ² (C ₂ -C ₄ ) alkylene; x is an integer between 1 and 500; Y = O, S, PH or NH; and R ^{3 is} hydrogen or a saturated or unsaturated linear or branched aliphatic, cycloaliphatic or aromatic (C ₁ -C ₃₀ ) hydrocarbon radical. 3. Polymers according to claim 1 and / or 2, characterized in that it is the comonomers B) are olefinically unsaturated acids and / or their salts with mono- and divalent counterions, particularly preferably acrylamidopropyl methylene sulfonic acid (AMPS); Esters of acrylic and (meth) acrylic acid with aliphatic, aromatic or cycloaliphatic alcohols with a Carbon number from 1 to 22; Esters of acrylic and (meth) acrylic acid with Alkyl ethoxylates, open-chain and cyclic N-vinylamides with a ring size of 4 up to 9 atoms; Amides of acrylic and methacrylic acid; 2-vinyl pyridine;  4-vinyl pyridine; Vinyl acetate; Methacrylic acid glycidyl ester; Acrylonitrile; Vinyl chloride; Vinylidene chloride; Tetrafluoroethylene and / or DADMAC. 4. Polymers according to at least one of claims 1 to 3, producible by radical copolymerization of

• A) one or more macromonomers selected from the group of the esters of (meth) acrylic acid with alkyl ethoxylates, which comprise 5 to 80 EO units and (C ₁₀ -C ₂₂ ) alkyl radicals, and
• B) one or more olefinically unsaturated comonomers selected from the group consisting of acrylamidopropylmethylene sulfonic acid (AMPS), sodium and ammonium salts of acrylamidopropylmethylene sulfonic acid (AMPS), acrylamide, N-vinylformamide, N-vinylmethylacetamide and sodium methallylsulfonate.

5. Polymers according to at least one of claims 1 to 4, characterized characterized in that the proportion of macromonomers is 50.1-99.9 mol%. 6. Polymers according to at least one of claims 1 to 4, characterized characterized in that the proportion of macromonomers is 0.1-50 mol%. 7. Polymers according to at least one of claims 1 to 6, characterized characterized by copolymerization of at least one crosslinker are crosslinked with at least two unsaturated double bonds. 8. Polymers according to at least one of claims 1 to 7, characterized characterized that they consist of a water-soluble polymer skeleton and Macromonomers A) with heat-sensitive side chains that contain an LCST in water Have behavior, exist, and the aqueous solution has a viscosity that above a certain threshold temperature increases with increasing temperature or remains approximately constant.   9. Polymers according to at least one of claims 1 to 7, characterized characterized in that their aqueous solution has a viscosity below a first threshold temperature is low, above this first threshold temperature increases with temperature to a maximum and above a second Threshold temperature drops again with increasing temperature. 10. Polymers according to at least one of claims 1 to 7, characterized characterized that their 1% aqueous solutions at room temperature Show viscosity of 20,000 mPas to 100,000 mPas and the solutions none Show thermoassociating behavior. 11. Polymers according to at least one of claims 1 to 10, characterized characterized in that they are prepared by precipitation polymerization in tert-butanol will. 12. Aqueous preparations, aqueous-alcoholic preparations, aqueous surfactant preparations, emulsions and suspensions containing polymers according to at least one of claims 1 to 11. 13. Preparations, emulsions and suspensions according to claim 12, characterized characterized that these are cosmetic and pharmaceutical agents acts. 14. Preparations, emulsions and suspensions according to claim 12 or 13, characterized in that they, based on the finished formulation, 0.05 to Contain 10 wt .-% of polymers. 15. Use of polymers according to at least one of claims 1 to 11 as a thickener, dispersant, suspending agent, emulsifier, stabilizer and / or Consistency generator.   16. Use of polymers according to at least one of claims 1 to 11 as adjuvants in crop protection formulations